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WO2008002037A1 - Colorants dichroïques réactifs, procédé de préparation de ces derniers, film à base de poly(alcool de vinyle) comprenant des colorants dichroïques réactifs et film polarisant - Google Patents

Colorants dichroïques réactifs, procédé de préparation de ces derniers, film à base de poly(alcool de vinyle) comprenant des colorants dichroïques réactifs et film polarisant Download PDF

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Publication number
WO2008002037A1
WO2008002037A1 PCT/KR2007/003046 KR2007003046W WO2008002037A1 WO 2008002037 A1 WO2008002037 A1 WO 2008002037A1 KR 2007003046 W KR2007003046 W KR 2007003046W WO 2008002037 A1 WO2008002037 A1 WO 2008002037A1
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WIPO (PCT)
Prior art keywords
nhch
coona
och
same
dichroic dye
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PCT/KR2007/003046
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English (en)
Inventor
Sang Hyun Baek
Sang Bong Park
E Joon Choi
Seung Sock Choi
Il Hyun Park
Jin Ho Jang
Eun Chul Kim
Si Min Kim
Original Assignee
Kolon Industries, Inc.
Kumoh National Institute Of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from KR1020060058076A external-priority patent/KR100995613B1/ko
Priority claimed from KR1020060128338A external-priority patent/KR100993896B1/ko
Application filed by Kolon Industries, Inc., Kumoh National Institute Of Technology filed Critical Kolon Industries, Inc.
Priority claimed from KR1020070061476A external-priority patent/KR100995610B1/ko
Publication of WO2008002037A1 publication Critical patent/WO2008002037A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
    • C09B62/08—Azo dyes
    • C09B62/09—Disazo or polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/106—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an azo dye
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines

Definitions

  • the present invention relates to a reactive dichroic dye, which includes a dihalotriazine group to thus be reactive to polyvinylalcohol , a method of preparing the reactive dichroic dye, which includes a dihalotriazine group to thus be reactive to polyvinylalcohol , a method of preparing the reactive dichroic dye, which includes a dihalotriazine group to thus be reactive to polyvinylalcohol , a method of preparing the
  • a plurality of dyes has been developed for various applications, including fabric dyeing, textile printing,
  • Such dyes are designed to have the molecular structure and bonding strength suitable for each application so as to impart essential properties, including hue, solubility, affinity for a substrate, chemical resistance, and
  • Dichroism is a property in which the orientation of assembled dye molecules has low absorption at a predetermined light wavelength in any one orientation state depending on the direction of polarization of a light source, and high absorption at the same wavelength in another orientation state.
  • dyes having such dichroism may also be applied to the development of polarizing films, in addition to fabric dyeing.
  • a dichroic dye is applied to the dyeing of a polyvinylalcohol (hereinafter, referred to as "PVA") film constituting the polarizer of a polarizing film.
  • PVA polyvinylalcohol
  • a typical PVA film, serving as the polarizer, is obtained through the iodine immersion method.
  • the iodine-doped PVA film is disadvantageous because it has high sublimation, drastically decreasing polarizing properties and durability, upon long exposure under conditions of high temperature and high humidity. Accordingly, instead of iodine, dyes having very low sublimation have been used.
  • Polarizing films that are presently commercially available may be classified into various types depending on the kind and performance thereof.
  • the iodine-based polarizing film has been chiefly used as a polarizing film for LCDs.
  • the phase difference film is a film for correcting a phase difference occurring in liquid crystals, and presently useful is a phase difference film made of polycarbonate.
  • a transflective polarizing film having both transmission properties and reflection properties.
  • the transflective polarizing film has an effect on power consumption efficiency, which is regarded as the most important factor in the display of a mobile apparatus. Because the lifespan of the product is undesirably decreased at high power consumption rates, in the LCD of the mobile apparatus, a conventional transmissive product having high power consumption has been replaced with a functional film useful as a material for the lower plate of a transflective LCD imparted with a reflection function using external light.
  • the transflective film types vary depending on the kind of material used and the properties thereof.
  • Exemplary are products (ST type) having adjusted transmittance through the addition of an adhesive with a pigment, and products composed of hundreds of polymer thin film layers having different refractive indexes.
  • Fifth there is a transflective polarizing film having high reflectance, which is a polarizing film having increased reflectance using a metal-deposited film and having an improved outer appearance using a diffusion adhesive, instead of the transflective polarizing film using a conventional pigment, in order to decrease the power consumption of an STN-LCD and to more clearly exhibit the outer appearance of the display, in recent years.
  • a polarizing film (AG/AR) for surface anti-reflection for surface anti-reflection. Surface anti- reflection includes anti-glare (AG) and anti-reflection (AR) .
  • the AG process is conducted by roughening the surface of a film to thus induce the diffuse reflection of external light from the surface thereof, so as to exhibit anti- reflection effects, and the AR process manifests anti- reflection effects by forming a thin film composed of a plurality of layers having different refractive indexes on the surface of a film through deposition or coating.
  • the reflectance of a polarizing film not subjected to AR processing is about 4%, and the AG film has reflectance of about 2%, and the AR film has reflectance less than 1%.
  • a reflective polarizing film which is a product obtained by laminating a metal-deposited reflective film on a general iodine-based polarizing film to thus make it suitable for use in reflective LCDs.
  • polarizing films include, as the polarizer thereof, a film having polarizing properties, in which PVA is treated with iodine or dichroic dye as mentioned above. Further, with the goal of preventing the deformation of the film due to the low durability and high sublimation of iodine, a protective layer is formed. To this end, the use of triacetyl cellulose, polyesters, polycarbonates, etc., which have no birefringence, high transmittance, no wavelength dependence, and high heat, moisture resistance and mechanical strength, is known. Moreover, it is known that the film may be treated with an adhesive and then the outermost surface thereof may be covered with a protective film. The principle of the polarizing film thus formed is as follows.
  • the polarizing film functions to convert natural light, which is incident while vibrating in various directions, into light (that is, polarized light) vibrating in only one direction.
  • the LCD uses the birefringence of liquid crystals, it is very important to control the direction of vibration of light incident on the liquid crystal molecules.
  • the function of the polarizing film is assured by stretching the PVA film and subjecting the stretched PVA film to dyeing and immersion in a solution of iodine or dichroic dye such that iodine molecules or dye molecules are arranged parallel to the stretching direction. Because the iodine or dye molecules are dichroic, the polarizing film may have the function of absorbing light vibrating in the stretching direction and transmitting light vibrating in the direction perpendicular thereto.
  • polarizing films which are presently available, are a PVA-I 2 based polarizing film obtained by immersing optical PVA in an aqueous solution of iodine and iodine-potassium complex to thus dye PVA, which is then uniaxially stretched about 400%.
  • the PVA has properties such as high linearity, high film formability, high crystalUnity, superior alkali resistance even at a pH of 13.5 or more, and high adhesion, so that a PVA-I 2 polarizing film for LCDs, which is presently commercialized, may exhibit sufficient electrical and optical performance.
  • the PVA-I 2 polarizing film has superior properties, it suffers because it has drastically deteriorated polarizing properties and durability, attributable to the high sublimation of iodine, when allowed to stand under conditions of high temperature and high humidity for a long period of time, undesirably causing problems in which a protective film must be applied on both surfaces of the film.
  • the present invention is intended to develop, in place of iodine, a dichroic dye, which includes a trihalotriazine group, thereby exhibiting optical properties similar to iodine and further improving durability while transmittance is not decreased.
  • a first embodiment of the present invention is to provide a novel reactive dichroic dye, which is reactive to PVA-based resin.
  • a second embodiment of the present invention is to provide a method of preparing the novel reactive dichroic dye.
  • a third embodiment of the present invention is to provide a PVA-based film, which includes the reactive dichroic dye, in which a dichroic dye is introduced with trihalotriazine, thus exhibiting superior transmittance, in particular, high durability, while maintaining polarizing properties .
  • the third embodiment of the present invention is to provide a PVA-based film having superior transmittance and improved durability while maintaining polarizing properties equal to those of an iodine-based polarizing film.
  • a fourth embodiment of the present invention is to provide a polarizing film having superior polarizing properties and transmittance and improved durability.
  • a reactive dichroic dye represented by Formula 1 below, having an azo chromophore and at least one amine group (-NH 2 ) at the end portion thereof, in which at least one hydrogen atom of the amine group is substituted with a halotriazine group:
  • A is , or
  • R 3 , R 4 , R 5 and R 6 which are same as or different from each other, are H, NH 2 , OH, SO 3 Na, CH 3 , OCH 3 , COONa, COOH, SO 2 NH 2 , SO 2 NHCH 3 , SO 3 Na, SO 3 CH 3 , NHCOCH 3 , NHCONH 2 , NHCH 2 SO 3 Na or NHCH 2 COONa, at least one of R 3 to R 6 being NH 2 ; R 7 , R 8 , R 9 and Rio, which are same as or different from each other, are H, NH 2 , OH, SO 3 Na, CH 3 or OCH 3 ; Rn and Ri 2 , which are same as or different from each other, are H, NH 2 , OH, SO 3 Na, CH 3 , OCH 3 , COONa, COOH, SO 2 NH 2 , SO 2 NHCH 3 , SO 3 Na, SO 3 CH 3 , NHCOCH 3 , NH,
  • Ri 3 to Ri 6 being ;
  • R 7 , R 8 , Rg and Rio are defined as above;
  • X 1 is a halogen group
  • H NH 2 , OH, SO 3 Na, CH 3 , OCH 3 , COONa, COOH, SO 2 NH 2 , SO 2 NHCH 3 , SO 3 Na, SO 3 CH 3 , NHCOCH 3 , NHCONH 2 , NHCH 2 SO 3 Na or NHCH 2 COONa, at least one of Ri 7
  • Ri8 being Rig, R 2 o and R 21 , which are same as or different from each other, are (wherein
  • Xi is a halogen group), H, NH 2 , OH, SO 3 Na, CH 3 , OCH 3 , COONa, COOH, SO 2 NH 2 , SO 2 NHCH 3 , SO 3 Na, SO 3 CH 3 , NHCOCH 3 , NHCONH 2 , NHCH 2 SO 3 Na or NHCH 2 COONa, at least one of Ri 9 to R 2i being
  • A may be any organic compound.
  • R 6 is NaSO 3
  • R i3 is , Ri 4 and Ri 5 are H
  • Ri6 is NaSO 3 .
  • A may be any organic compound.
  • R 2 is NaSO 3
  • X is NH
  • R 7 is OH
  • R 8 and R 9 are H
  • R i0 is NaSO 3
  • Rn and Ri 2 are NH 2 , Ri 7 is , and Ri 8 is NH 2 .
  • A may be any organic compound.
  • Ri 9 is OH, R 9 and Ri 0 are SO 3 Na, Rn and Ri 2 are H, Ri 9 is
  • R 20 is CH 3
  • R 2 i is NH 2 .
  • Xi may be Cl.
  • a method of preparing a reactive dichroic dye including reacting a dichroic dye represented by Formula 2 below, having an azo chromophore and at least one amine group at the end portion thereof, with a trihalotriazine compound represented by Formula 3 below, thus preparing a reactive dichroic dye represented by Formula 1 below, having an azo chromophore and at least one amine group
  • R 3 , R 4 , R 5 and Re which are same as or different from each other, are H, NH 2 , OH, SO 3 Na, CH 3 , OCH 3 , COONa, COOH, SO 2 NH 2 , SO 2 NHCH 3 , SO 3 Na, SO 3 CH 3 , NHCOCH 3 , NHCONH 2 , NHCH 2 SO 3 Na or NHCH 2 COONa, at least one of R 3 to R 6 being NH 2 ;
  • R 7 , Rs, Rg and Ri 0 which are same as or different from each other, are H, NH 2 , OH, SO 3 Na, CH 3 or OCH 3 ;
  • Rn and Ri 2 which are same as or different from each other, are H, NH 2 , OH, SO 3 Na, CH 3 , OCH 3 , COONa, COOH, SO 2 NH 2 , SO 2 NHCH 3 , SO 3 Na, SO 3 CH 3 , NHCOCH 3 , NHCON
  • Xi is a halogen group
  • H NH 2 , OH, SO 3 Na, CH 3 , OCH 3 , COONa, COOH
  • R 8 , Rg and Rio are defined as above; Ri 7 and Ris, which are same as or different from each other, are
  • Xi is a halogen group) , H, NH 2 , OH, SO 3 Na, CH 3 , OCH 3 , COONa, COOH, SO 2 NH 2 , SO 2 NHCH 3 , SO 3 Na, SO 3 CH 3 , NHCOCH 3 , NHCONH 2 ,
  • the reaction may be conducted at 10 to 30°C for 20 to 30 hours.
  • the reaction may be conducted using one or more solvents selected from among dimethylformamide (DMF) , dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP) .
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • NMP N-methylpyrrolidone
  • a PVA-based film including the reactive dichroic dye represented by Formula 1 below, having an azo chromophore and at least one amine group (-NH 2 ) at the end portion thereof, in which at least one hydrogen atom of the amine group is substituted with a halotriazine group:
  • R 3 , R 4 , R 5 and Re which are same as or different from each other, are H, NH 2 , OH, SO 3 Na, CH 3 , OCH 3 , COONa, COOH, SO 2 NH 2 , SO 2 NHCH 3 , SO 3 Na, SO 3 CH 3 , NHCOCH 3 , NHCONH 2 , NHCH 2 SO 3 Na or NHCH 2 COONa, at least one of R 3 to R 6 being NH 2 ;
  • R 7 , Rs, Rg and Rio which are same as or different from each other, are H, NH 2 , OH, SO 3 Na, CH 3 or OCH 3 ;
  • Rn and Ri 2 which are same as or different from each other, are H, NH 2 , OH, SO 3 Na, CH 3 , OCH 3 , COONa, COOH, SO 2 NH 2 , SO 2 NHCH 3 , SO 3 Na, SO 3 CH 3 , NHCOCH 3 , NHCONH 2
  • Xi is a halogen group
  • H NH 2 , OH, SO 3 Na, CH 3 , OCH 3 , COONa, COOH
  • Ri 7 (wherein Xi is a halogen group) , H, NH 2 , OH, SO 3 Na, CH 3 , OCH 3 , COONa, COOH, SO 2 NH 2 , SO 2 NHCH 3 , SO 3 Na, SO 3 CH 3 , NHCOCH 3 , NHCONH 2 , NHCH 2 SO 3 Na or NHCH 2 COONa, at least one of Ri 7
  • Xi is a halogen group), H, NH 2 , OH, SO 3 Na, CH 3 , OCH 3 , COONa, COOH, SO 2 NH 2 , SO 2 NHCH 3 , SO 3 Na, SO 3 CH 3 , NHCOCH 3 , NHCONH 2 , NHCH 2 SO 3 Na or NHCH 2 COONa, at least one of R 19 to R 2i being
  • dichroic dye may be B thereof may be
  • Ri and R 2 are H, R 3 is NH 2 , R 4 and R 5 are H, Re is NaSO 3 , Ri 3 is
  • Ri4 and Ri5 are H, and Ri 6 is NaSO 3 .
  • a of the reactive dichroic dye may be , B thereof may be
  • Ri is H
  • R 2 is NaSO 3
  • X is NH
  • R 7 is OH
  • R 8 and R 9 are H
  • Ri 0 is NaSO 3
  • Rn and Ri 2 are
  • Ri 7 is , and R 18 is NH 2 .
  • dichroic dye may be , B thereof may be
  • R 2 are H, R 7 is NH 2 , R 8 is OH, R 9
  • Xi of the reactive dichroic dye may be Cl.
  • a polarizing film including the PVA-based film.
  • a polarizing film having increased transmittance, in particular, superior durability, while maintaining polarizing efficiency may be provided.
  • FIG. 1 illustrates the IR (KBr pellet) spectrum of Congo Red, which is the dichroic dye
  • FIG. 2 illustrates the NMR (DMSOd 6 ) spectrum of Congo Red, which is the dichroic dye
  • FIG. 3 illustrates the IR (KBr pellet) spectrum of the reactive dichroic dye having a chlorotriazine group, synthesized in Example 1 according to the present invention
  • FIG. 4 illustrates the NMR (DMSO-d 6 ) spectrum of the reactive dichroic dye having a chlorotriazine group, synthesized in Example 1 according to the present invention
  • FIG. 5 illustrates the IR (KBr pellet) spectrum of Direct Black 22, which is the dichroic dye
  • FIG. 6 illustrates the NMR (DMSOd 6 ) spectrum of Direct Black 22, which is the dichroic dye,-
  • FIG. 7 illustrates the IR (KBr pellet) spectrum of the reactive dichroic dye having a chlorotriazine group, synthesized in Example 2 according to the present invention
  • FIG. 8 illustrates the NMR (DMSOd 6 ) spectrum of the reactive dichroic dye having a chlorotriazine group, synthesized in Example 2 according to the present invention
  • FIG. 9 illustrates the IR (KBr pellet) spectrum of Direct Black 4, which is the dichroic dye
  • FIG. 10 illustrates the NMR (DMSOd 6 ) spectrum of Direct Black 4, which is the dichroic dye
  • FIG. 11 illustrates the IR (KBr pellet) spectrum of the reactive dichroic dye having a chlorotriazine group, synthesized in Example 3 according to the present invention
  • FIG. 12 illustrates the NMR (DMSO-d 6 ) spectrum of the reactive dichroic dye having a chlorotriazine group, synthesized in Example 3 according to the present invention
  • FIG. 13 is a graph illustrating the transmittance and polarizing efficiency of the iodine-adsorbed PVA film (Comparative Example 1) ;
  • FIG. 14 is a graph illustrating the transmittance and polarizing efficiency of the Congo Red-dyed PVA film (Comparative Example 2);
  • FIG. 15 is a graph illustrating the transmittance and polarizing efficiency of the Direct Black 22-dyed PVA film (Comparative Example 3) ;
  • FIG. 16 is a graph illustrating the transmittance and polarizing efficiency of the Direct Black 4-dyed PVA film (Comparative Example 4)
  • FIG. 17 is a graph illustrating the transmittance and polarizing efficiency of the PVA film (Example 4) prepared through the reaction with the reactive dichroic dye of Example 1 according to the present invention
  • FIG. 18 is a graph illustrating the transmittance and polarizing efficiency of the PVA film (Example 5) prepared through the reaction with the reactive dichroic dye of Example 2 according to the present invention
  • FIG. 19 is a graph illustrating the transmittance and polarizing efficiency of the PVA film (Example 6) prepared through the reaction with the reactive dichroic dye of Example 3 according to the present invention.
  • FIG. 20 is a graph illustrating the results of evaluation of the durability of the iodine-adsorbed PVA film (Comparative Example 1)
  • FIG. 21 is a graph illustrating the results of evaluation of the durability of the Congo Red-dyed PVA film (Comparative Example 2) ;
  • FIG. 22 is a graph illustrating the results of evaluation of the durability of the Direct Black 22-dyed PVA film (Comparative Example 3) ;
  • FIG. 23 is a graph illustrating the results of evaluation of the durability of the PVA film (Example 4) , prepared through the reaction with the reactive dichroic dye of Example 1 according to the present invention;
  • FIG. 24 is a graph illustrating the results of evaluation of the durability of the PVA film (Example 5) , prepared through the reaction with the reactive dichroic dye of Example 2 according to the present invention.
  • FIG. 25 is a graph illustrating the results of evaluation of the durability of the PVA film (Example 6) , prepared through the reaction with the reactive dichroic dye of Example 3 according to the present invention
  • the present invention relates to a novel reactive dichroic dye, the novel reactive dichroic dye of the present invention having a halotriazine group, and being specifically represented by Formula 1.
  • the reactive dichroic dye represented by Formula 1 In the reactive dichroic dye represented by Formula 1,
  • A may be or , in which Ri and R 2 is a hydrogen atom. In any case, at least one of Ri and R 2 may be NaSO 3 . Further, in the reactive dichroic dye represented by
  • Formula 1, B may be , in which R 3 is NH 2 and R 4 is NaSO 3 .
  • the preferred substitution position is 2,6- or 1,4-.
  • the linear substitution position is favorable for maintaining the linearity of molecules, and the linearity of molecules may positively affect the orientation of molecules when a film is stretched.
  • B may be , in which R 7 is OH, Rs and Rg are H, Rg is NaSO 3 , and both Rn and Ri 2 are NH 2 . Also, in the reactive dichroic dye represented by
  • Formula 1, B' may be in which R 13 is
  • B' may be , in which R 7 ,
  • R 8 , Rg and R 1O are defined as above, and R 17 is
  • Formula 1 , B' may be , in which R 1 and R 2 are H, R 7 is NH 2 , Rs is OH, R 9 and R 10 are SO 3 Na, R 11 and R 12 are H, R 19 is
  • Xi is a halogen atom, preferably, Cl, Br or F, and more preferably Cl.
  • the reactive dichroic dye represented by Formula 1 may be obtained by reacting a dichroic dye represented by Formula 2, having an azo chromophore and at least one amine group at the end portion thereof, with a trihalotriazine compound represented by Formula 3.
  • R 13 ' , Ri 4 ' , Ri 5 ' and Ri 6 ' which are the same as or different from each other, are H, NH 2 , OH, SO 3 Na, CH 3 , OCH 3 , COONa, COOH, SO 2 NH 2 , SO 2 NHCH 3 , SO 3 Na, SO 3 CH 3 , NHCOCH 3 , NHCONH 2 , NHCH 2 SO 3 Na or NHCH 2 COONa, at least one of Ri 3 ' to Ri 6 ' being NH 2 ; R 7 , R 8 , R 9 and Ri 0 are defined as above; Ri 7 ' and Ris', which are the same as or different from each other, are H, NH 2 , OH, SO 3 Na, CH 3 , OCH 3 , COONa, COOH, SO 2 NH 2 , SO 2 NHCH 3 , SO 3 Na, SO 3 CH 3 , NHCOCH 3 , NHCONH 2 , NHCH 2 SO 3
  • dichroic dye represented by Formula 2 include Congo red, Direct Black 4, 17, 19 and 22, Direct Red 2 and 28, Direct Blue 1 and 15, and Direct Violet 12.
  • trihalotriazine compound represented by Formula 3 examples include 2,4, 6-trichloro-l,3, 5- triazine (cyanuric chloride), 1,2,3- and 1,2,4-triazine or triazine derivatives, such as melamine and benzoguanamine.
  • the reaction ratio of the dichroic dye to the trihalotriazine compound represented by Formula 3 may range from 1:0.9 to 1:1.5.
  • the reaction may take place at 10 to 3O 0 C for 20 to 30 hours.
  • a solvent such as dimethylformamide (DMF), dimethylacetamide (DMAc) , or N-methylpyrrolidone (NMP) may be used.
  • an additive such as triethylamine or pyridine, may be further added, if necessary.
  • the solid precipitate is removed through filtration, and the solvent is removed using a vacuum distillation device. The residue obtained after the removal of the solvent is washed with alcohol, filtered, and vacuum dried at 40 ⁇ 60°C, thus obtaining the reactive dichroic dye represented by Formula 1 according to the present invention.
  • the structure of the reactive dichroic dye product may be confirmed using FT-IR and 1 H-NMR spectroscopy.
  • FT-IR and 1 H-NMR spectroscopy because the expected value of the product after the completion of the reaction is not greatly different from that of the mixture of the reaction materials, it is difficult to estimate the extent of progress of the reaction.
  • the product is thoroughly washed using alcohol, which is a solvent of the reaction materials, but is not a solvent of the product, until there is no change in the weight thereof, thus indicating the complete removal of unreacted materials, followed by performing spectroscopy.
  • the PVA- based film is immersed, yielding a PVA-based film according to the present invention.
  • the immersion method is not particularly limited, but is exemplarily conducted in a manner such that the reactive dichroic dye is dissolved in water and then the PVA-based film is immersed in the dye solution.
  • the reactive dichroic dye is dissolved to a concentration of 0.0001 to 10 wt% in water, thus preparing a salt bath.
  • the pH is preferably set within the range from 8 to 12.
  • the PVA-based film colored with the reactive dichroic dye is washed with an aqueous solution to thus eliminate the residual reactive dichroic dye.
  • stretching is conducted, thereby obtaining the PVA-based film in which the dichroic dye molecules are arranged parallel to the stretching direction.
  • the stretching may be conducted through a wet process or a dry process, or alternatively, before the dyeing, a process of stretching the PVA-based film may be adopted.
  • post-treatment including boric acid treatment, may be conducted to improve beam transmittance, the degree of polarization and light resistance of the polarizing film.
  • boric acid treatment may vary depending on the type of dye used, it may be conducted at
  • Example 1 A better understanding of the present invention may be obtained through the following examples, which are set forth to illustrate, but are not to be construed as the limit of the present invention.
  • Example 1 A better understanding of the present invention may be obtained through the following examples, which are set forth to illustrate, but are not to be construed as the limit of the present invention.
  • the dichroic dye used as the starting material and the product were confirmed using FT-IR and 1 H-NMR spectroscopy.
  • FIGS. 1 and 2 The results of FIGS. 1 and 2 are summarized as follows.
  • Direct Black 22 [4] (2.9 g, 2.7 x 10 "3 mol, available from CiBA specialty chemicals) was added with dimethylformamide (25 ml) to thus be dissolved at room temperature in a nitrogen atmosphere, after which cyanuric chloride (0.5 g, 2.7 x 10 ⁇ 3 mol) was added to the solution in which Direct Black 22 was dissolved. After 1 min, 0.38 ml (2.7 x 10 "3 mol) of triethylamine was added in droplets thereto. Stirring was then performed at 20 0 C for 24 hours. After the completion of the reaction, the solid precipitate was removed through filtration using a filter device, and the solvent was removed using a vacuum distillation device. The residue obtained after the removal of the solvent was washed with ethanol, filtered again, and vacuum dried at 60°C, thus obtaining a compound [5] .
  • the reaction route of the compound thus obtained is schematically represented by Scheme 2 below.
  • the dichroic dye used as the starting material and the synthesized product were confirmed using FT-IR (300E FT/IR spectrometer available from Jasco) , and 1 H-NMR spectroscopy (DPX 200MHx NMR spectrometer available from Bruker) .
  • FIGS. 5 and 6 The results of FIGS. 5 and 6 are summarized as follows. IR (KBr ) v max (cm l ) : 3416, 1610, 1412, 1112, 1030.
  • FIGS. 7 and 8 are summarized as follows.
  • Direct Black 4 (1.88 g, 2.7 x ICT 3 mol, available from Aldrich) was added with dimethylformamide (25 ml) to thus be dissolved at room temperature in a nitrogen atmosphere, after which cyanuric chloride (0.5 g, 2.7 x 10 ⁇ 3 mol) was added to the solution in which Direct Black 4 was dissolved. After 1 min, 0.38 ml (2.7 x lO ""3 mol) of triethylamine was added in droplets thereto. Stirring was then performed at 20°C for 24 hours. After the completion of the reaction, the solid precipitate was removed through filtration using a filter device, and the solvent was removed using a vacuum distillation device. The residue obtained after the removal of the solvent was washed with ethanol, filtered again, and vacuum dried at 6O 0 C, thus obtaining a compound [7] .
  • the reaction route of the compound thus obtained is schematically represented by Scheme 3 below.
  • the dichroic dye used as the starting material and the product were confirmed using FT-IR and 1 H-NMR spectroscopy.
  • FIGS. 9 and 10 are summarized as follows.
  • Examples 1 and 3 was prepared, dissolved to a concentration of 1 wt% in 100 ml of distilled water, added with 1 wt% of Na 2 SO 4 to increase the adsorption of the dye, and added with
  • a 4 cmx 4 cm sized PVA film which was washed with distilled water and dried, was allowed to react for 30 min. After the completion of the reaction, the PVA was washed with distilled water, further washed several times with an aqueous solution having a pH adjusted to 11 and distilled water to remove the unreacted doped dye, and then stretched five times in a 2 wt% aqueous boric acid solution. The stretched film was vacuum dried at 40°C for 24 hours.
  • a typical iodine-dyed PVA film was prepared.
  • the preparation of the iodine-dyed PVA film was as follows.
  • PVA was simply washed with distilled water.
  • 0.1 M iodine (I) and 0.2 M potassium iodide (KI) were dissolved in 100 ml of distilled water at 4O 0 C.
  • the PVA film was immersed for 2 min.
  • the iodine (I) which was not doped, was removed through washing using cold distilled water.
  • the PVA-I 2 sample film thus obtained was vacuum dried in an oven at 4O 0 C for 24 hours.
  • the dichroic dye As the starting material of the reactive dichroic dye of each of Examples 1 to 3, the dichroic dye was prepared, dissolved to a concentration of 0.5 wt% in 100 ml of distilled water, and added with 1 wt% of Na2SO4 to increase the adsorption of the dye.
  • a 4 cm x 4 cm sized PVA film which was washed with distilled water and dried, was immersed for 120 sec. After the completion of the immersion, the resultant PVA was washed with distilled water, further washed several times with distilled water to remove the dye, which was not doped but remained on the surface thereof, and then stretched four times in a 2 wt% aqueous boric acid solution. The stretched film was vacuum dried at 40°C for 24 hours .
  • optical properties of the film were determined by measuring the UV-Vis absorption spectrum using an S-1100, available from Scinco.
  • transmittance value transmittance at a maximum absorption wavelength was used.
  • the single-film transmittance at a maximum absorption wavelength was determined to be 42.8%, and the polarizing efficiency was calculated to be 99.8%.
  • FIG. 14 illustrating the optical properties of the Congo Red-dyed PVA film (Comparative Example 2), the single- film transmittance at a maximum absorption wavelength was determined to be 11.3%, and the polarizing efficiency was calculated to be 99.9%.
  • FIG. 16 illustrating the optical properties of the Direct Black 4-dyed PVA film (Comparative Example 4)
  • the single-film transmittance at a maximum absorption wavelength was determined to be 7.5% and the polarizing efficiency was calculated to be 88.4%.
  • FIG. 17 illustrating the optical properties of the PVA film (Example 4) obtained using the reactive dichroic dye of Example 1 according to the present invention, the single- film transmittance at a maximum absorption wavelength was determined to be 25.3%, and the polarizing efficiency was calculated to be 98.4%.
  • FIG. 18 illustrating the optical properties of the PVA film (Example 5) obtained using the reactive dichroic dye of Example 2 according to the present invention, the single- film transmittance at a maximum absorption wavelength was determined to be 34.8%, and the polarizing efficiency was calculated to be 82.7%.
  • FIG. 19 illustrating the optical properties of the PVA film (Example 6) obtained using the reactive dichroic dye of Example 3 according to the present invention, the single- film transmittance at a maximum absorption wavelength was determined to be 17.8%, and the polarizing efficiency was calculated to be 98.8%.
  • the PVA film (Example 4) obtained using the reactive dichroic dye of Example 1 was evaluated to have high polarizing efficiency of 98.4% and the PVA film (Example 5) obtained using the reactive dichroic dye of Example 2 exhibited slightly high polarizing efficiency of
  • the test was carried out in a desiccator under conditions of temperature of 50°C and humidity of 85% or more for five days, and changes in transmittance and polarizing efficiency were measured at intervals of 24 hours.
  • FIG. 20 illustrates the results of evaluation of the durability of the PVA-I 2 film (Comparative Example 1) .
  • FIG. 21 illustrates the results of evaluation of the durability of the Congo Red-dyed PVA film (Comparative Example 2)
  • FIG. 22 illustrates the results of evaluation of the durability of the Direct Black 22-dyed PVA film (Comparative Example 3)
  • FIG. 23 illustrates the results of evaluation of the durability of the PVA film (Example 4) using the dye of Example 1
  • FIG. 24 illustrates the results of evaluation of the durability of the PVA film (Example 5) using the dye of Example 2
  • FIG. 25 illustrates the results of evaluation of the durability of the PVA film (Example 6) using the dye of Example 3.
  • the transmittance was changed from 25.3% to 30.5%, and the rate of change was 5.8%. That is, the changes in polarizing efficiency and transmittance were not greater than in the case of the iodine-based polarizing film.
  • the initial polarizing efficiency of 82.7% was changed to 77.0% after 120 hours.
  • the initial polarizing efficiency of 98.8% was changed to 94.8%, and the rate of change was 4.0%.
  • Transmittance was changed from 17.9% to 43.5%, and the rate of change was 25.6%. From this, even though the dyed film (Comparative Example 1) had excellent polarizing efficiency, the very poor transmittance thereof before the durability test was made much worse after the durability test, making it impossible to use the above film in practice.
  • the PVA film obtained through the reaction of the reactive dichroic dye according to the present invention could be seen to have relatively lower rates of change.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polarising Elements (AREA)

Abstract

L'invention concerne un nouveau colorant dichroïque réactif. Lorsque le colorant dichroïque réactif est utilisé pour la préparation d'un film polarisant, un film polarisant présentant une transmittance accrue, en particulier, une durabilité supérieure, et conservant une efficacité de polarisation peut être préparé.
PCT/KR2007/003046 2006-06-27 2007-06-22 Colorants dichroïques réactifs, procédé de préparation de ces derniers, film à base de poly(alcool de vinyle) comprenant des colorants dichroïques réactifs et film polarisant WO2008002037A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR10-2006-0058076 2006-06-27
KR1020060058076A KR100995613B1 (ko) 2006-06-27 2006-06-27 반응성 이색성 염료 및 그 제조방법
KR1020060128338A KR100993896B1 (ko) 2006-12-15 2006-12-15 반응성 이색성 염료를 포함하는 폴리비닐알코올계 필름 및편광필름
KR10-2006-0128338 2006-12-15
KR10-2007-0061476 2007-06-22
KR1020070061476A KR100995610B1 (ko) 2007-06-22 2007-06-22 반응성 이색성 염료, 그 제조방법, 반응성 이색성 염료를포함하는 폴리비닐알코올계 필름 및 편광필름

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WO2008002037A1 true WO2008002037A1 (fr) 2008-01-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009120643A (ja) * 2007-11-12 2009-06-04 Mitsubishi Chemicals Corp 異方性色素膜用色素

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001240762A (ja) * 1999-12-24 2001-09-04 Sumitomo Chem Co Ltd アゾ化合物又はその塩及びそれらを含有する染料系偏光膜
WO2004085547A1 (fr) * 2003-03-26 2004-10-07 Rolic Ag Colorants azoiques dichroiques polymerisables
JP2005171231A (ja) * 2003-11-17 2005-06-30 Sumitomo Chemical Co Ltd ポリアゾ化合物又はその塩、及び該化合物又はその塩を有する偏光膜
WO2005106542A1 (fr) * 2004-04-30 2005-11-10 Ace Digitech, Ltd. Film optique et colorant pour dispositif d'affichage a ecran plat
EP1614719A1 (fr) * 2003-04-16 2006-01-11 Nippon Kayaku Kabushiki Kaisha Compose azoique et sel correspondant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001240762A (ja) * 1999-12-24 2001-09-04 Sumitomo Chem Co Ltd アゾ化合物又はその塩及びそれらを含有する染料系偏光膜
WO2004085547A1 (fr) * 2003-03-26 2004-10-07 Rolic Ag Colorants azoiques dichroiques polymerisables
EP1614719A1 (fr) * 2003-04-16 2006-01-11 Nippon Kayaku Kabushiki Kaisha Compose azoique et sel correspondant
JP2005171231A (ja) * 2003-11-17 2005-06-30 Sumitomo Chemical Co Ltd ポリアゾ化合物又はその塩、及び該化合物又はその塩を有する偏光膜
WO2005106542A1 (fr) * 2004-04-30 2005-11-10 Ace Digitech, Ltd. Film optique et colorant pour dispositif d'affichage a ecran plat

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009120643A (ja) * 2007-11-12 2009-06-04 Mitsubishi Chemicals Corp 異方性色素膜用色素

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